Sulfosuccinic acid semi-esters of oxyalkylated polynuclear alkyl-phenols

ABSTRACT

This invention relates to sulfosuccinic acid semi-esters of oxyalkylated polynuclear alkylphenols of the formula   IN WHICH R represents a group of the formula   (OX) represents oxyalkylene radicals, R1 represents an alkyl group having 6 to 14 carbon atoms, Y represents hydrogen or has the same meaning as that given for R , n represents a number from 2 to 25, z represents a number from 1 to 9 and Me stands for hydrogen or an alkali metal, and their use as dispersing and wetting agents for sprayable powders or dispersable concentrates containing water-insoluble organic biocidal agents.

United States Patent [191 Grossmann et al.

[111 3,888,828 June 10, 1975 SULFOSUCCINIC ACID SEMI-ESTERS OF OXYALKYLATED POLYNUCLEAR ALKYL-PHENOLS [73] Assignee: Hoechst Aktiengesellschaft,

Frankfurt am Main, Germany [22] Filed: June 29, 1972 [21] Appl. No.: 267,512

[30] Foreign Application Priority Data June 30, 1971 Germany 2132405 [52] US. Cl. 260/49; 71/79; 71/93;

[51] Int. Cl C08g 5/18 [58] Field of Search 260/49 [56] References Cited UNITED STATES PATENTS 2,454,542 1 1/1948 Bock et al 260/49 2,663,698 12/1953 Compton 260/49 3,137,713 6/1964 Shen et a1. 260/400 3,210,291 10/1965 Kirkpatrick et al... 252/335 3,293,214 12/1966 Feeman 260/49 3,442,859 5/1969 Lipowski et al. 260/49 Primary Examiner-Lester L. Lee Attorney, Agent, or Firm-Curtis, Morris & Safford [57] ABSTRACT This invention relates to sulfosuccinic acid semi-esters of oxyalkylated polynuclear alkylphenols of the for mula in which R represents a group of the formula OC-CH CH-COOMe 0r OC-CH-CH -COOMe l i l (OX) represents oxyalkylene radicals, R represents an alkyl group having 6 to 14 carbon atoms, Y represents hydrogen or has the same meaning as that given for R n represents a number from 2 to 25, z represents a number from 1 to 9 and Me stands for hydrogen or an alkali metal, and their use as dispersing and wetting agents for sprayable powders or dispersable concentrates containing water-insoluble organic biocidal agents.

5 Claims, No Drawings SULFOSUCCINIC ACID SEMI-ESTERS OF OXYALKYLATED POLYNUCLEAR ALKYL-PHENOLS Organic water-insoluble biocidal agents are often used in the form of so-called spray powders. These spray powders are powdery preparations of biocidal agents which are applied in the form of aqueous suspensions. In order to permit easy application, the suspensions must have a good suspension and wetting property. In addition to the active substance (biocidal agent), the spray powders in general contain carrier substances such as aluminium or magnesium silicates or synthetic silicic acids and optionally adhesives and, in addition, wetting and dispersing agents. The content of active substance in the spray powders may vary within wide limits; it amounts in most cases to about 20 to 80 percent by weight. The proportion of wetting and dispersing agents in the spray powders is in general about 0.5 to 8 percent by weight.

Typical examples of organic biocidal agents are, for example, chlorohyrocarbons such as DDT, Lindan, Chlordan, Aldrin, Dieldrin, Endrin and Toxaphen, and phosphoric acid esters such as Parathion, Methylparathion, Malathion, Trithion and Systox as well as carbamates such as Carbaryl and similar compounds.

It is already known from US. Pat. No. 3 236 627 that sulfosuccinic acid semi-esters of oxalkylated alkylphenols are suitable dispersing agents for waterinsoluble biocidal agents. However, the dispersing action of these known compounds is often considered as insufficient.

The present invention provides sulfosuccinic acid semi-esters of oxalkylated polynuclear alkyl-phenols, a process for preparing them and their use as dispersing and wetting agents for water-insoluble organic biocidal agents.

The sulfosuccinic acid semi-esters of oxalkylated polynuclear alkyl-phenols of the present invention are compounds of the general formula I in which R represents a group of the formula -OC-CH -CH-COOMe or -OCCHCH COOMe SO Me $O Me (OX) represents oxyalkylene radicals, in particular oxyethylene and/or oxypropylene, R1 represents a saturated, straight chain or branched alkyl group having 6 to 14 carbon atoms, Y represents hydrogen or has the same meaning as that given for R, n represents a number from 2 to 25, z represents a number from 1 to 9 and Me stands for hydrogen or an alkali metal.

The present invention furthermore provides dispersable concentrates of water-insoluble organic biocidal agents which contain sulfosuccinic acid semi-esters of oxalkylated polynuclear alkyl-phenols of the formula I as dispersing or wetting agents.

For preparing the sulfosuccinic acid semi-esters of oxalkylated polynuclear alkyl-phenols of the formula I, mono-alkyl-phenols of the formula OH 1 y are condensed with formaldehyde in a molar ratio of 2 1 to 10 9 according to known methods (ef. Hultzsch, Chemie der Phenolharze, 1950, page 114) in the presence of acid catalysts to yield novolak resins, these resins are reacted with 2 to 25 moles, referred to each phenol group, of alkylene-oxide according to known methods, preferably in the presence of alkaline catalysts, whereupon novolak resin oxalkylates are obtained whose free hydroxyl groups are then totally or partially esterified, at 20 to C, with maleic acid anhydride to yield maleic acid semi-esters which are finally reacted in aqueous phase with water-soluble salts of sulfurous acid to yield sulfosuccinic acid semiesters.

For the formation of the novolak resins, there may be used as mono-alkyl-phenols of the formula for example hexyl-, heptyl-, octyl-, nonyl-, dodecylor tetradecyl-phenol or mixtures of these alkyl-phenols, the alkyl groups optionally being straight chain or branched groups. In the reaction, formaldehyde in form of an aqueous solution or of para-formaldehyde may be used. The acid catalysts may be mineral acids such as sulfuric acid, phosphoric acid or, owing to the fact that it can be easily eliminated during removal of the water by distillation, preferably hydrochloric acid. In general, the acids are used in a concentration of 0.1 to 5 percent by weight, referred to the alkyl-phenol. The condensation is effected at temperatures in the range of from about 20 to 150 C, preferably from 80 to C, suitably under an' atmosphere of nitrogen. The water present after the condensation is then removed by distillation to a residual content in the novolak resin of less than 0.5 percent by weight. This operation is carried out finally under reduced pressure of less than 50 Torr.

The novolaks obtained constitute more or less brittle, clear, yellow-brown coloured resins in the form of big blocks. They are mixtures of polynuclear alkyl-phenols which are linked by methylene bridges. Their composition depends above all on the ratio of alkyl-phenol to formaldehyde.

The oxalkylation of the novolak resins is carried out according to known methods with ethylene oxide or 1,2-propylene oxide or ethylene oxide and propylene oxide in the presence of alkaline catalysts at about 100 to 210 C, preferably at to C. As alkaline catalysts, there may be used above all alkali metal hydroxides such as potassium hydroxide or, preferably, sodium hydroxide, or alkali metal-alkoxides such as sodium methylate or sodium ethylate. These alkaline catalysts are preferably used in a concentration of 0.05 to 1.0 percent by weight, referred to the novolak resin. The oxalkylation may be effected without pressure or in pressure vessels and the alkylene oxide may be introduced either in gaseous or liquid form. The alkylene oxide is used in such an amount that 2 to 25 moles of alkylene oxide groups are introduced per each phenolic hydroxyl groups. It is preferred to use 3 to 15 moles of ethylene oxide per mole of starting alkyl-phenol.

The reaction of the novolak oxalkylate with maleic acid anhydride to yield the maleic acid semi-ester is carried out by mixing the components and stirring them at about 20 to 100C, preferably at 40 to 80C, in the presence of alkalis, preferably alkali metal hydroxides. These alkaline catalysts are used in a concentration of about 0.05 to 1.0 percent by weight, referred to the novolak oxalkylates. Since maleic acid anhydride tends to sublimation, it is advantageous to carry out the reaction in pressure vessels under a pressure of about 0.2 to 1.0 atmosphere gauge of nitrogen or air and to ensure thorough mixing, because at the beginning the molten maleic acid anhydride can not easily be mixed with the novolak oxalkylates. The maleic acid anhydride may be used in such an amount that all novolak oxalkylate hydroxyl terminal groups or a part thereof, at least however one terminal hydroxyl group of the novolak oxalkylate, are reacted.

Transformation of these maleic acid semi-ester compounds into the corresponding sulfo-succinic acid semi-esters is effected in an aqueous medium by reaction with water-soluble sulfites or hydrogen sulfites. The sulfites or hydrogen sulfites, preferably alkali metal or alkaline earth metal sulfites -bisulfites or -pyrosulfites are used in quantities of about 1.0 to 1.5 mole, preferably 1.05 to 1.1 mole, calculated as sulfurous acid per maleic acid semi-ester group. For this reaction, the di-alkali metal sulfites are particularly suitable, since they lead to the formation of dialkali metal salts of the sulfosuccinic acid semi-esters.

.The quantity of water added during the reaction may amount to 50 to 85 percent by weight, referred to the total solution or mixture. It depends on the solubility of the sulfosuccinic acid semi-ester salts and on the viscosity of the solutions. The reaction temperatures are kept at about 20 to 100 C, preferably at 40 to 80 C.

For their use as dispersing and wetting agents, the sulfosuccinic acid semi-ester salts of the present invention may be applied optionally without purification directly in the form of their solutions. If desired the aqueous solutions of the sulfosuccinic acid semi-ester salts may also be dehydrated according to known methods, for example by spray-drying. This spray drying may also be carried out in the presence of other components, for example pyrogenic silicic acid. The salts of the sulfosuccinic acid semi-esters of oxalkylated novolak resins are sticky to solid substances; they are excellent wetting and dispersing agents with moderate foam formation and are therefore particularly suitable for biocidal spray powders. For this purpose the amount of wetting and dispersing agents may be in the range of 0.5 to 8 percent by weight.

The following Examples describe the preparation of the sulfo-succinic acid semi-esters of the formula 1, the preparation of mono-nuclear comparative substances and comparative tests of these substances as dispersing agents in spray powders on the basis of water-insoluble organic biocidal agents.

A. Preparation of the Sulfosuccinic Acid Semi-Esters of Oxalkylated Novolak Resins a. Preparation of the Novolak Resins z+l Moles of alkyl-phenol and 2 moles of formaldehyde were mixed at room temperature and, after addition of 0.55 percent by weight of concentrated hydrochloric acid ((1 1.18), referred to the alkyl-phenol, stirred for 4 hours at 95106 C under reflux. Then, the water is removed by distillation, while working finally under a reduced pressure of about 20 to 2 Torr.

b. Oxalkylation of the Novolaks and Preparation of the Maleic Acid Semi-Esters 1 Mole of the novolak resin was combined with 0.2 percent by weight of sodium hydroxide, referred to the novolak resin, and (1+1 )-n moles of ethylene oxide and/or propylene oxide were added at 150l60 C. The oxalkylate was then reacted at 5080 C, while stirring and after addition of 0.1 percent by weight of sodium hydroxide, referred to the novolak oxethylate, with z 1 moles or at least 1 mole of maleic acid anhydride to yield the maleic acid semi-esters (n and z having the meanings given above).

0. Preparation of the Sulfosuccinic Acid Semi-Esters into the solution of the maleic acid semi-ester within' about minutes at 40 to C. When the batch had become clearly soluble in water, stirring was continued for 1 hour. The total quantity of water added during the reaction wa 50 to 80 percent by weight, referred to the solution of the sulfosuccinic acid semi-ester obtainedafter completion of the reaction.

The values for the compounds of the formula 1 prepared according to this method are indicated in Tables Ia and lb.

Table Ia Ex- Starting Novolak Ethylene- Maleic acid- Maleic acid semi-ester ample OH OH oxide anhydride Na SO 71-1 0 Refrac- Acid number 2 H tion Found Calc.

index R R Z V p25 Mole R 2 Mole (z+1)-n Mole Mole 1 C l-1, 1 1 6 2 1.5153 137.0 122.5 2.2 2 l l 12 2 1.5078 96.7 95.4 2.2 3 1 1 21 2 1.4987 79.2 70.8 2.2 4 1 1 12 1 1.5025 50.8 50.7 1.1

Table Ia Continued Ex- Starting Novolak Ethylene- Maleic acid- Maleic acid semi-ester angle OH OH oxide anhydride Na SO 7H O Refrae- Acid number CH H tion Found Calc.

indegc 1 "n R,

. Mole 1 z Mole (z+1)-n Mole Mole Table Ib Ex- Starting Novolak Ethylene- Maleic acid- Maleic acid semi-ester Na SO 7H O ample oxide, or anhydrid Refrac- No. Propylenetion Acid Number oxide index Found Cale.

R 2 Mole Mole Mole n 11 C H 3 1 4 1.5190 113.5 116.5 4.4 12 3 1 18 4 1.5168 108.8 106.4 4.4 13 3 1 21 4 1.5129 107.0 100.0 4.4 14 8 1 54 9 1.5111 102.6 94.4 9.9 15 2 1 6O 3 1.4881 50.4 46.6 3.3 16 8 1 224 9 FP34.535.5 40.4 39.3 9.9

C 17 Q 11 2 1 24 3 1.5050 76.6 77.5 3.3 18 2 1 6 PO 3 1.5056 89.1 88.9 3.3

12 E0 1) 19 2 1 6 PO 3 1.4992 90.5 90.5 3.3

12 E0 2) 20 C H 4 1 27 E0 5 1.5134 107.4 107.1 5.5

,1) At first 6 moles PO (=propylene oxide), then 12 E0 (ethylene-oxide) (Block-oxalkylate) 2) A mixture of 6 moles PO and 12 mol E0 added (mixed oxalkylate with statistical distribution of the P0 and E0 groups).

B. Preparation of Sulfosuccinic Acid Semi-Esters of Oxyethylated Mono-Nuclear Mono-Alkyl-Phenols (Comparative Substances V and W) n Moles of ethylene oxide were added, at 140160 C, to 1 mole of alkyl-phenol in the presence of 0.2 percent by weight of sodium hydroxide, referred to the alkyl-phenol. The oxethylate was then reacted at -80 C, while stirring thoroughly, with 1 mole of maleic acid anhydride. 1.05 mole to 1.1 mole of sodium sulfite in the form of an aqueous solution were stirred within about minutes into the aqueous solution of the maleic acid semi-ester obtained. When the batch had be-- come clearly soluble in water, the whole was further stirred for 1 hour at the indicated temperature. The total quantity of water present in the solution obtained was found to be 50 to percent by weight.

The dates of the compounds obtained are indicated in Table 11.

TABLE I1 The determination of the wetting power was carried out as follows: a glass beaker having a capacity of 500 ml (8 cm diameter) was filled with tap water of 20 C and a hardness of 12dH (German hardness) and 1 gram of the spray powder to be tested was strewn on the surface. The time which is required for wetting the powder is measured and indicated in seconds as wettingr time.

(comparative product):

Pro- Start- Moles Ethy- Maleic Maleic acid semi-ester Na SO 71-1 0 duking leneacid Refraction Acid number ts phenol oxide anindex hydrid found calc. Mole Mole n Mole V Mono- 1 6.0 1.0 1.4980 102.2 95.6 1.1

nonyl- W phenol 1 9.7 1.0 1.4932 78.5 75.2 1.1

In the tests regarding application, the dispersing and wetting properties and the foaming behaviour of the The test for the foaming property was carried out according to J. Ross and G. D. Miles (cf. Oil and Soap 18 7 8 (1941), 99) with a concentration of 4 grams of the D, spray powder to be tested per liter of water at a quan- 20% by weight of Dieldrin tity measured in of 500 ml. The height of the foam in 77% by weight of siliceous chalk cm was measured at the beginning and after a period 3% by weight of wetting and dispersing agent. of time of minutes. 5

The results of these comparative tests are compiled The following spray powder formulations were used in Tables In to VI.

for the comparative tests with the wetting and dispersing agents to be tested: A.

50% by weight of Lindan 37% by weight of siliceous chalk 10% by weight of silicic acid 3% by weight of wetting and dispersing agent.

A comparison of the results indicated in Tables III and VI with those of Table VII shows above all the superior outstanding dispersing power (suspending power) and often also a better wetting power of the sulfosuccinic acid semi-esters of exalkylated novolaks of the present invention (Examples 1 to 19) over that of the sulfosuccinic acid semi-esters of mono-nuclear 50% by PF mono-alkylphenols (comparative substances V and 37% by weight of siliceous chalk 10% by weight of silicic acid 3% by weight of wetting and dispersing agent. Further tests with the wetting and dispersing agents C. according to Example 2 of Table Ia show that these 30% by weight of Endosulfan novel dispersing and wetting agents are also excellently 64% by weight of siliceous chalk suitable for formulations with those active substances 3% by weight of silicic acid which are difficult to wet. The results of these tests are 3% by weight of wetting and dispersing agent. contained in Table VIII.

Table III Wetting and dispersing power of sulfosuccinic acid semi-esters of oxethylated binuclear novolaks (Example Nos. 1 4) in spray powder formulations.

Spray Suspension property in Wetting power in secs. R M Foam (immediately/after 5 mins.)

powder Wetting and dispersing agents Example current nos. of Table la) formulations A 91 9O 91 90 10 15 1O 17 4.5/3.5 10.0/9.5 9.0/8.5 B 78 83 77 78 15 10 20 2.0/0.1 4.0/3.5 4.0/3.5 C 85 85 83 75 1O 15 10 E5 2.5/2.0 5.0/4.5 8.0/7.5 D 83 89 88 81 10 15 1O 15 3.5/3.0 8.0/7.0 10.0/9.5

Table IVa Wetting and dispersing power of sulfosuccinic acid semi-esters of oxethylated trinuclear novolaks (Example Nos. 5 9) in spray powder formulations.

Spray SuspensIon property in Wetting power in secs. R M foam (immediately/after 5 mins.)

powder formuwetting and dispersing agents Example current nos. of Table Ia.

lations A 95 92 91 90 86 20 20 25 20 3.0/2.0 3.0/2.0 4.0/3.0 4.5/4.0 4.5/4.0 B 71 79 77 75 76 20 20 20 15 1.5/0.5 2.0/1.0 2.5/1.5 2.5/1.0 2.5/0.5 C 83 86 83 84 78 15 15 15 15 20 2.5/1.5 2.5/l.5 2.5/1.5 4.5/2.5 4.5/2.5 D 88 90 90 87 86 15 15 10 10 25 4.0/2.0 4.5/2.5 4.5/2.5 4.5/2.5 4.5/2.5

Table IVb Wetting and dispersing power of sulfosuccinic acid semi-esters of oxalkylated trinuclear novolaks (Example Nos. 15, 17 19) in spray powder formulations.

Spray Suspension property in Wetting power in secs. R M foam (immediately/after 5 mins.)

powder formula- Wetting and dispersing agents Example current nos. of Table 1b.

tions A 71 90 89 10 60 17 23 25/10 35/20 3.5/3.0 3.5/3.0 B 58 82 78 15 50 20 35 20/05 2.0/0.5 1.5/0.5 1.0/1.0 C 66 86 80 80 10 25 12 12 2.5/l.0 2.5/l.0 2.0/1.0 2.0/1.0 D 75 90 84 83 15 30 15 15 30/10 20/10 2.0/1.0 3.0/2.0

Table V Wetting and dispersing power of sulfosuccinic acid semi-esters of oxcthylatcd Novolak with 4 nuclei (Example Nos. 10 13) in spray powder f rmulations. Spray Suspension property in Wetting power in secs. R M foam (immediately after mtns.)

powder f l;

I Wetting and dispersing agents Example current nos. to Table la and lb.

l0 ll 12 l3 ll l2 l3 l0 1] l2 l3 A 88 86 88 88 20 2t) 20 .5 3.5/2.0 3.5/2.0 4.5/3.5 B 68 7 l 7] 71 20 20 25 25 2.5/1.0 2.5/1.0 2.5/1.0 3.0/2.0 C 82 X1 Kl 80 l5 15 l5 l5 1.5/0.0 3.0/l.0 3.0/l.0 3.5/2.0 D )0 J l 9] 90 l5 20 l5 l5 2.0/0.5 2.0/0.5 2.5/I .0 3.0/2.0

Table Vl Wetting and dispersing power of sulfosuccinic acid semies spray powder formulations.

ters of oxethylated novolaks with 9 nuclei (Examples 14 and 16) in Spray Suspension property in Wetting power in secs. R M foam immediately/after 5 mins) powder 4 g formu- Wetting and dispersing agents lzxample current nos. of Table lb.

lations l4 l6 l4 l6 l4 16 A 87 93 (i0 55 4.5/4.0 B 70 7) 55 95 2.0/0.5 C 80 X5 65 2.0/0.5 D 86 X8 70 2.5/l.0

Table Vll Wetting and dispersing behaviour of the comparative substances V and W (according to Table ll) in spray powder formulations.

Spray Suspension property in 71' Wetting power in secs. R M foam powder in cm formula- Comparative substances according to Table ll. (immediately/after tions 5 mins.)

V W V W V W A 22 20 20 l9.5/l5.0 l5.0/l l.() B Bl 35 20 20 8.5/7.0 7.5/6.5 22 l5 15 20 l4.0/l3.0 [3.5/1 15 l) 35 2X 20 20 l5.0/l l.5 l4.0/l2.0

TABLE Vlll A comparison of the values indicated in Tables lll to Wetting and dispersing behaviour of the 2 of'lablc la in fomiulations with active to wet.

Spray powder formulations product according to Example substances which are diflicult Suspension property in 7n Wetting power in seconds All'lllltl siliceous chalk silicic acid wetting and dispersing agent according to Example 2 Simazin siliceous chalk -l silicic acid wetting and dispersing agent according to lixamplc 2 ('aplan siliceous chalk l silicia acid wetting and dispersing agent according to lixaulplc 2.

Zineb siliceous chalk -l silieic acid wettin I and dispersing agent accortiing to Example 2.

VI to those given in Table VI] shows that the sulfosuc cinic acid semicsters of oxalkylated novolaks of the invcntion, prepared from mono-alkyl-phcnols and formaldehyde (Examples l to 19) have above all an outstanding dispcrsing power (suspending property) and partly also a better wetting power over the sulfosuccinic semi-esters of mono-nuclear mono-alkylphenols (comparative substances V and W).

Since in biocidal spray powders a strong foam formation of the dispersing and wetting agents is a considerable disadvantage in the use of these spray powders. the advantageous low tendency to foam formation of the compounds of the invention should be particularly pointed out.

The utilization of the sulfosuccinic acid semi-esters of the formula I as dispersing and wetting agents in the preparation of spray powders on the basis of waterinsoluble organic biocidal agents is a preferred application of this sulfosuccinic acid semi-ester. ln addition thereto. these compounds are excellently suitable as dispersing and emulsifying agents also for other purposes, for example for preparing emulsion concentrates of water-insoluble organic biocidal agents. The amount of wetting and dispersing agents may be in the range of l to 30% by weight of the emulsion concentrate. In this case, the sulfosuccinic acid semi-esters may be used alone or with other, preferably non-ionogenic emulsifiers, for example the reaction products of ethyleneoxide with lipophilic compounds. The following examples of emulsifiable concentrates of organic biocidal agents are intended to illustrate this use of the sulfosuccinic acid semi-esters of the present invention.

EXAMPLE 21 in which R represents a group of the formula O Me Ol' SO Me (OX) represents oxyethylene, oxypropylene and mixture thereof, R represents a saturated straight chain or branched alkyl group having 6 to 14 carbon atoms, Y represents hydrogen or has the same meaning as that given for R, n represents a number from 2 to 25, 1 represents a number from 1 to 9 and Me stands for hydrogen or an alkali metal.

2. The polynuclear compound of claim 1 having the formula wherein R is selected from the group consisting of -o iir-uoo-na b L 2 kl,

and

-oc-cn,cu -r.ooua

SO Na 3 Z is equal to l and (Z-H )'n is equal to 21.

3. The polynuclear compound of claim 1 having the formula (0C H -0R 2 n wherein R is selected from the group consisting of Z is equal to 2 and (Z+1 )'n is equal to 18.

4. The polynuclear compound of claim 1 having the formula 2 (oc u OK H (211 wherein R is selected from the group consisting of -0C-CH -CH-COONa SO Na 3 and 0C-CH-CH2-COONa S0 Na 3 Z is equal to 8 and (Z+l )'n is equal to 224.

5. The polynuclear compound of claim 11. having the formula R (LCF. -OR

wherein R is selected from the group consisting of 14 -OCCH -CH-CONa and -0C-CH-C1-; -CO0Na so Na Z is equal to 2 and (Z+1)'n is equal to 24. 

1. SULFOSUCCINIC ACID SEMI-ESTERS OF OXALKYLATED POLYNUCLEAR ALKYL-PHENOLS OF THE GENERAL FORMULA 1
 2. The polynuclear compound of claim 1 having the formula
 3. The polynuclear compound of claim 1 having the formula
 4. The polynuclear compound of claim 1 having the formula
 5. The polynuclear compound of claim 1 having the formula 